7042 J . Org. Chem., Vol. 66, No. 21, 2001
Zhao et al.
3.83 (m, 8 H), 3.76-3.69 (m, 12 H), 1.79-1.71 (m, 8 H), 1.55-
1.43 (m, 8 H). MS (EI): m/z 837 (M + H)+. Anal. Calcd for
C48H56O11N2: C, 68.55; H, 6.76; N, 3.02. Found: C, 68.87; H,
6.76; N, 3.35. Compound 9b was then treated with hydrazine
in hot ethanol to afford compound 10b in 92% yield as a white
solid after workup. Mp: 266-268 °C. 1H NMR (CDCl3): δ 7.02
(m, 8 H), 5.11 (s, 4 H), 4.22 (m, 4 H), 4.08 (t, 4 H), 3.99 (m, 4
H), 3.89 (m, 8 H), 3.11 (m, 4 H), 1.97-1.82 (m, 8 H), 1.71-
1.62 (m, 8 H). MS (EI): m/z 576 (M+). Anal. Calcd for
CN in 27% yield as a red solid following the procedure
described for 19a ‚4Cl after anion exchange with ammonium
hexafluorophosphate. Mp: 166 °C dec. 1H NMR (DMSO-d6):
δ 9.49 (d, 8 H), 8.41 (d, 8 H), 7.99 (s, 8 H), 8.05 (br, 2 H), 7.57
(br, 2 H), 7.24-7.17 (m, 30 H), 5.91 (s, 8 H), 3.81-3.35 (m, 36
H), 3.08 (br, 4 H), 1.74 (br, 4 H), 1.44 (br, 12 H). MS (ESI):
m/z 1035.5 (M - 2PF6)2+, 642 (M - 3PF6)3+, 445 (M - 4PF6)4+
.
Anal. Calcd for C114H122O11N8P4F24‚4H2O: C, 56.27; H, 5.52;
N, 4.52. Found: C, 56.28; H, 5.40; N, 4.60.
C
32H52O7N2‚H2O: C, 64.61; H, 9.17; N, 4.71. Found: C, 64.29;
[2]Rota xa n e 20a . A solution of isophthaloyl dichloride 15
(2.03 g, 10.0 mmol) in anhydrous chloroform (50 mL) and a
solution of p-xylylenediamine 16 (1.36 g, 10.0 mml) in anhy-
drous chloroform (50 mL) were added simultaneously over a
period of 5 h at room temperature with stirring to a solution
of compound 11a (1.20 g, 1.02 mmol) and triethylamine (2.76
mL, 20.0 mmol) in anhydrous chloroform (50 mL). The mixture
was then stirred at room temperature for another 12 h. The
solid was filtered off. The filtrate was washed with 1 N HCl
solution (3 × 100 mL), 5% NaHCO3 solution (3 × 100 mL),
water (100 mL), and brine (100 mL) and then dried over
anhydrous sodium sulfate. The solvent was evaporated in
vacuo, and the resulting residue was purified by chromatog-
raphy (silica gel, 20:1 CHCl3/CHOH) to give [2]rotaxane 20a
(0.31 g, 18%) as a white solid. Mp: 108-110 °C. 1H NMR
(CDCl3): δ 8.19 (s, 2 H), 8.12 (d, 4 H), 7.56 (m, 2 H), 7.45 (s,
4 H), 7.28-7.13 (m, 30 H), 7.00 (s, 8 H), 6.71-6.62 (m, 8 H),
6.50 (br, 2 H), 5.70 (br, 2 H), 4.43 (s, 8 H), 3.93 (s, 4 H), 3.71
(m, 8 H), 3.57 (m, 8 H), 3.53 (s, 4 H), 2.98 (m, 8 H), 1.68 (m, 4
H). MS (ESI): m/z 1709 (M+). Anal. Calcd for C104H106O15N8‚
H2O: C, 72.30; H, 6.26; N, 6.02. Found: C, 72.36; H, 6.32; N,
6.49.
[2]Rota xa n e 17. The compound was prepared in 19% yield
as a white solid from the reaction of compounds 6, 15, and 16
in chloroform by using a procedure similar to that described
in the preparation of rotaxane 20a . Mp: 197-198 °C. 1H NMR
(1:2 CD3OD/CDCl3): δ 8.19 (s, 2 H), 8.08 (d, 4 H), 7.58 (t, 2
H), 7.48 (s, 4 H), 7.26-7.13 (m, 30 H), 7.07 (s, 8 H), 6.62 (s, 4
H), 4.42 (s, 8 H), 3.68 (t, 4 H), 3.48 (s, 4 H), 3.02 (s, 4 H), 2.90-
2.99 (m, 4 H), 1.67 (m, 4 H). MS (ESI): m/z 1463 (M + Na)+.
Anal. Calcd for C90H86O10N8‚2H2O: C, 73.56; H, 6.18; N, 7.59.
Found: C, 73.24; H, 6.16; N, 7.59.
[2]Rota xa n e 20b. The rotaxane was prepared in 18% yield
as a white solid from the reaction of 11b, 15, and 16 in
chloroform by using a procedure similar to that described in
the preparation of rotaxane 20a . Mp: 94-95 °C. 1H NMR
(CDCl3): δ 8.18 (s, 2 H), 8.09 (d, 4 H), 7.53 (m, 6 H), 7.28-
7.13 (m, 30 H), 7.05 (s, 8 H), 6.74 (s, 8 H), 6.50 (br, 1 H), 5.70
(br, 1 H), 4.45 (s, 8 H), 3.96 (t, 4 H), 3.79 (t, 4 H), 3.73 (s, 4 H),
3.58 (s, 4 H), 3.02 (br, 3 H), 2.77 (br, 3 H), 2.00 (br, 2 H), 1.63
(m, 4 H), 1.25 (m, 10 H), 1.11 (m, 4 H). MS (ESI): m/z 1793
(M + H)+. Anal. Calcd for C110H118O15N8: C, 73.53; H, 6.81;
N, 5.95. Found: C, 73.71; H, 6.65; N, 6.24.
[3]Rota xa n e 21a ‚4Cl. This [3]rotaxane was prepared in
54% yield as a red solid from the reaction of compounds 12‚
2PF6 and 13 in the presence of [2]rotaxane 20a by using a
procedure similar to that described in the preparation of 19a ‚
4Cl. Mp: 110 °C dec. 1H NMR (DMSO-d6): δ 9.90 (br, 4 H),
9.78 (br, 4 H), 9.49 (br, 4 H), 8.78 (br, 4 H), 8.67 (br, 4 H), 8.20
(s, 2 H), 8.14 (d, 4 H), 7.99 (s, 8 H), 7.67 (t, 2 H), 7.31 (s, 8 H),
7.19 (s, 32 H), 6.60 (br, 2 H), 5.92 (br, 8 H), 4.95 (d, 4 H), 4.26
(d, 4 H), 3.93-2.72 (m, 40 H), 1.96 (br, 2 H), 1.68 (br, 2 H).
MS (ESI): m/z 1149 (M - 2Cl)2+, 754 (M - 3Cl)3+, 557 (M -
4Cl)4+. Anal. Calcd for C140H138O15N12Cl4‚4H2O: C, 68.83; H,
6.04; N, 6.88. Found: C, 68.47; H, 6.20; N, 6.84.
H, 9.27; N, 4.69.
Com p ou n d 11a . A suspension of DCC (1.80 g, 8.70 mmol),
amino acid derivative 5 (2.70 g, 7.50 mmol), and diamine 10a
(1.80 g, 3.66 mmol) in THF (150 mL) was stirred at room
temperature for 24 h. The solid was filtered off, and the filtrate
was evaporated to give a solid residue. The residue was
purified by chromatography (silica gel, 20:1 dichloromethane/
ethanol) to give compound 11a (2.58 g, 59%) as a white power.
Mp: 89-90 °C. 1H NMR (CDCl3): δ 7.26-7.24 (m, 30 H), 6.83-
6.75 (m, 8 H), 6.24 (br, 2 H), 5.86 (br, 2 H), 4.03 (t, 4 H), 3.82
(m, 8 H), 3.69 (m, 8 H), 3.57 (s, 4 H), 3.50 (s, 4 H), 3.24 (d, 4
H), 1.82 (m, 4 H). MS (ESI): m/z 1175 (M+). Anal. Calcd for
C
72H78O11N4: C, 73.06; H, 6.83; N, 4.64. Found: C, 73.57; H,
6.69; N, 4.77.
Com p ou n d 11b. This compound was prepared in 51% yield
as a white solid starting from compounds 5 and 10b according
to a procedure similar to that described above for compound
11a . Mp: 84-85 °C. 1H NMR (CDCl3): δ 7.26-7.18 (m, 30
H), 6.84-6.76 (m, 8 H), 6.05 (br, 2 H), 5.89 (br, 2 H), 4.03 (t,
4 H), 3.83 (m, 8 H), 3.72 (m, 8 H), 3.60 (s, 4 H), 3.50 (d, 4 H),
3.05 (d, 4 H), 1.67 (m, 8 H), 1.32 (m, 8 H). MS (ESI): m/z 1259
(M+). Anal. Calcd for C78H90O11N4: C, 74.36; H, 7.07; N, 4.35.
Found: C, 74.37; H, 7.22; N, 4.45.
[2]Rota xa n e 19a ‚4Cl. Compound 11a (2.28 g, 1.94 mmol),
5
dicationic compound 12‚2PF6 (0.28 g, 0.40 mmol), and dibro-
mide 13 (0.10 g, 0.40 mmol) were dissolved in CH3CN (30 mL)
and CHCl3 (30 mL). The solution was stirred for 12 days at
ambient temperature. After the solvent was removed under
reduced pressure, the residue was subjected to column chro-
matography (silica gel), which was first treated with 10:1
CHCl3/C2H5OH as an eluent to elute the neutral compounds,
with a 2 N aqueous solution of 7:1:2 CH3OH/CH3NO2/NH4Cl
as the eluent. The orange product fractions were combined,
and the solvent was removed under reduced pressure. The
residue was washed with cold water completely to give
[2]rotaxane 19a ‚4Cl (0.26 g, 36%) as a red solid. Mp: 166 °C
1
dec. H NMR (CD3OD): δ 9.23 (d, 8 H), 8.17 (s, 8 H), 7.89 (s,
8 H), 7.28-7.14 (m, 30 H), 6.80-6.30 (br, 4 H), 5.98 (s, 8 H),
3.92-3.30 (m, 36 H), 1.90 (br, 4 H). MS (ESI): m/z 1802 (M -
Cl)+, 883 (M - 2Cl)2+. Anal. Calcd for C108H110O11N8Cl4‚4H2O:
C, 67.85; H, 6.41; N, 5.83. Found: C, 67.90; H, 6.24; N, 5.86.
[2]Rota xa n e 14‚4Cl. The compound was prepared as a red
solid in 20% yield starting from compounds 6, 12‚2PF6, and
13 by using a procedure similar to that described in the
preparation of 19a ‚4Cl. Mp: 171 °C dec. 1H NMR (CD3OD):
δ 9.29 (d, 8 H), 8.28 (d, 8 H), 7.91 (s, 8 H), 7.29-7.13 (m, 30
H), 5.73 (s, 8 H), 3.88 (s, 4 H), 3.67 (s, 4 H), 3.44 (br, 4 H),
3.31 (s, 4 H), 3.23 (br, 4 H), 2.02 (br, 4 H). MS (ESI): m/z 749
(M - 2Cl)2+, 487 (M - 3Cl)3+, 356 (M - 4Cl)4+. Anal. Calcd
for C94H90O6N8Cl4‚4H2O: C, 68.76; H, 6.03; N, 6.83. Found:
C, 68.42; H, 6.14; N, 6.79.
[3]Rota xa n e 18‚4Cl. This [3]rotaxane was prepared in 31%
yield as a red solid from the reaction of compounds 12‚2PF6
and 13 in the presence of [2]rotaxane 17 by using a procedure
similar to that described in the preparation of 19a ‚4Cl. Mp:
1
172 °C dec. H NMR (DMSO-d6): δ 9.82 (br, 8 H), 9.49 (br, 4
[3]Rota xa n e 21b‚4Cl. This [3]rotaxane was prepared in
47% yield as a red solid from the reaction of compounds 12‚
2PF6 and 13 in the presence of [2]rotaxane 20b by following
the procedure described for preparing 19a ‚4Cl. Mp: 168 °C
H), 8.68 (br, 10 H), 8.00 (s, 2 H), 7.97 (s, 4 H), 7.94 (s, 8 H),
7.60 (br, 2 H), 7.35 (s, 8 H), 7.23-7.13 (m, 32 H), 5.86 (s, 8 H),
4.92 (br, 4 H), 4.23 (d, 4 H), 3.80 (s, 2 H), 3.67 (br, 4 H), 3.07-
3.02 (m, 4 H), 2.73 (s, 4 H), 2.27 (s, 4 H), 1.89-1.78 (m, 4 H),
1.24 (s, 2 H). MS (ESI): m/z 490 (M - 4Cl)4+. Anal. Calcd for
1
dec. H NMR (CD3OD): δ 9.94 (br, 4 H), 9.31 (br, 4 H), 8.87
(br, 4 H), 8.24 (br, 4 H), 8.18 (s, 2 H), 7.99 (s, 12 H), 7.59 (t, 2
H), 7.34 (s, 8 H), 7.20 (m, 30 H), 6.30 (d, 2 H), 6.15 (d, 2 H),
6.03 (d, 4 H), 5.89 (d, 4 H), 4.96 (d, 4 H), 4.30 (d, 4 H), 3.99 (m,
8 H), 3.81-3.35 (m, 20 H), 3.10 (m, 4 H), 2.61 (br, 2 H), 2.39
(m, 2 H), 1.36 (m, 2 H), 1.13-1.08 (m, 8 H), 0.50 (m, 2 H),
C
126H118O10N12Cl4‚4H2O: C, 69.59; H, 5.85; N, 7.73. Found: C,
69.25; H, 6.08; N, 7.69.
[2]Rota xa n e 19b‚4P F 6. This [2]rotaxane was prepared
from the reaction of 11b, 12‚2PF6, and dibromide 13 in CH3-